Source apportionment of volatile organic compounds during paddy-residue burning season in north-west India reveals large pool of photochemically formed air toxics

Abstract

Paddy-residue burning is associated with poor air quality in north-west India during October–November every year. However, till date a quantitative study of its contribution to ambient volatile organic compounds (VOCs) using highly time-resolved measurements within the region has been lacking. Several VOCs like benzene are carcinogenic and also fuel formation of secondary pollutants such as secondary organic aerosol (SOA) and ozone. Here, we undertake quantitative source-apportionment using a PMF source-receptor model on a high-quality in-situ measured dataset of 54 VOCs in Punjab, India, and validate the model results using source profiles. The contribution of the seven most dominant sources to the total VOC mass concentrations were: daytime photochemistry and biogenic VOCs (BVOCs) (26%), followed by solid-fuel usage and waste-disposal (18%), traffic (two-wheeler 14% and four-wheeler 10%), photochemically aged biomass burning (17%), industries and solvent usage (9%), and fresh paddy residue burning (6%). Ozone production potential was dominated by solid fuel usage and waste disposal (25%), followed by traffic (two-wheeler 11% and four-wheeler 12%), BVOCs and photooxidation products (21%), photochemically aged biomass burning (16%), industries & solvent usage (9%) and fresh paddy residue burning (6%). SOA production was dominated by traffic (two-wheeler 26% and four-wheeler 28%) followed by solid fuel usage and waste disposal (22%), photochemically aged biomass burning emissions (15%) with minor contribution from industries & solvents (6%), fresh paddy residue burning (2%) and photochemistry and biogenic VOCs (1%). Comparisons with global emission inventories REASv3.2.1 and EDGARv4.3.2, showed both overestimate the industry and solvent source. Further, EDGARv4.3.2 underestimated the traffic source whereas paddy residue burning emissions are absent in REASv3.2.1. Although the overall mass contribution of paddy-residue burning emissions isn't high, our results show that health-relevant compounds emitted directly and formed photochemically from biomass burning sources active at this time are majorly responsible for the unhealthy air.